Correction process and coating composition therefor



Oct. 4, 1966 R. D. BITTING ETAL CORRECTION PROCESS AND COATING COMPOSITION THEREFOR FiledOct. 4, 1965 APPLY COATING OVER ERRONEOUS PORTION OF COPY MATERIAL DRY APPLIED COATING IMPRINT CORRECTION ON vDRY APPLIED COATING PHOTOGRAPH TO OBTAIN NEGATIVE ON WHICH ERRONEOUS PORTION AND COATING ARE NONDISCERNIBLE IN VE N TORS KENNETH E. JACKSON MELVIN C. KOCH RUSSELL D. BITTING ATTORNEY United States Patent M 3,276,870 CORRECTION PROCESS AND COATING COMPOSITION THEREFOR Russell D.. Bittiug, Naperville, Ill., and Melvin C. Koch and Kenneth E. Jackson, Columbus, .Ohio, assignors to The Battelle Development Corporation, Columbus,

Ohio, a corporation of Delaware Filed Oct. 4, 1965, Ser. No. 508,614 3 Claims. (Cl. 96-27) This application is a continuation-in-part of copending .application Serial No...747,720, filed July 10, 1958, now abandoned, which is a continuation-in-part of application Serial No. 360,598, filed June 9, 1953, and now abandoned.

This invention relates to a coating composition and a process utilizing the same. More specifically, it relates to a correction-fluid composition and process for the correction of typewritten or other printed material.

Typewritten or printed material is frequently duplicated by being photographed, and subsequently using the photographic negative to prepare a plate suitable for use in an offset or similar printing process. In such a process, many copies can be prepared, each having the clarity of the original copy.

It is obvious that any errors in the original copy must be completely eradicated, since high-contrast photographic negatives are used in this process. The correction of these errors has presented a serious problem.

It has been customary to correct errors in typewritten copy by preparing additional copy correctly typewritten. Both the incorrect and correct copies are taken to a cutting table, and the error is cut from the incorrect sheet. The corrected material is cut out so as to fit that space. The correction is placed in position and fixed by a transparent adhesive tape or other suitable means. The corrected copy is then ready to be photographed.

Since it is difficult to cut the correction accurately, so that the insert will exactly fit the space it is to cover, there are frequently areas of overlap or voids which will photograph as lines. In order to prevent these lines from appearing on the final reproductions, they must be removed from the photographic negative by opaquing. The lines are .usually close to the copy to be reproduced, and thus the opaquing step is deliberate and time-consuming.

It has now been found that the novel composition of this. invention can be applied over typewritten material, and that it will mask the coated, typewritten material to make the same photographically nondiscernible. It has further been found that this composition dries very quickly, and additional material may be typewritten over the coating after the expiration of this drying time.

Accordingly, one of the objects of this invention is to provide a process for quickly and easily correcting errors in typewritten. copy which is to be subsequently photographed. A further objcctis to provide a correction-fluid masking composition. Another object is to provide a coating material for paper, which coating resembles in color and appearance the paper when photographed. Other objects and advantageous features will be apparent from the following detailed description.

In the drawing, the single figure is a flow diagram illustrating the processof correction of a printed erroneous portion of a copy material'to obtain a negative on which the" erroneous portion and the coating thereover are photographically nondiscernible.

' Referring to the drawing, which illustrates the process of the invention by a flow diagram, the numeral designates the step of applying a coating over an erroneous portion of a copy material, the numeral 11 designates the step of drying the applied coating, the numeral 12 designates the step of imprinting acorrection on the dry ap- 3,276,870 Patented Oct. 4, 1966 plied coating, and the numeral 13 designates the step of photographingthe copy material, so treated, to obtain a negative on which the erroneous portion and the coating are photographically nondiscernible.

In general, the process of the invention comprises applying'a thin coating of the correction-fluid composition of the invention over an erroneous printed portion of a copy material, drying the applied coating, imprinting a correction on the dry applied coating, and photographing the copy material to obtain a negative on which the erroneous portion and the coating are photographically nondiscernible.

Applying of the thin coating may be by any of the conventional means such as spraying, brushing, etc. Preferably for ready commercial application the correctionfluid is supplied in a container having a brush afiixed to portions of the copy material.

Drying of the applied coating occurs rapidly at normal room temperature conditions without assistance of supplemental drying aids, such as heat. Preferably drying occurs within less than one minute and generally in about 30 seconds. Some variation in drying time is obtainable by proper selection of the organic solvent.

Imprinting of the correction on the dry applied coating is done by conventional means, such as typing, and generally by the same imprinting means by which the original erroneous and correct copy material was prepared.

Photographing of the copy material, so treated, is performed in a conventional manner to produce a negative. Photographing in this application is used in the meaning of including xerographic reproduction where by electrostatic means an image of the copy material is produced on a plate instead of the negative as in photographing. Copies then may be prepared from the negative by the usual means. Generally a plate (i.e., duplicating plate) is prepared from the negative and the copies prepared from this plate.

Customarily a large number of copies are then produced from the negative. It is desirable that these copies be clear, distinct, and void of any incorrect portions of copy material, and that these copies clearly, distinctly,

and accurately show only the originally correct copyma- 1 and without necessary or time consuming opaquing of the negative for production of flawless and completely accurate original copy material.

In general t-he correction-fluid coating composition of the invention comprises two essential components, namely an organic solvent and solid material. The solid material comprises a resinous, lacquer-type, film forming plastic or polymeric binder and an opaque pigment.

The binder material is preferably soluble in low boiling solvents. It must also be capable of forming a flexible film when it is deposited on a surface in solution and then subsequently air dried. In addition, it should contain at least one polar group per monomeric unit. Examples of suitable polar groups are:

-C1, --NO -OH, etc. Binder materials such as methyl acrylate-methyl methacrylate copolymers, shellac,

. 3 vinyl chloride-vinyl acetate copolymers, cellulose acetate, styrene-butadiene copolymers, etc. can be used. Suitable plasticizers may be combined with the binder material to reduce embrittlement so as to prevent chipping or flaking off of the coating.

Since the most satisfactory photographic reproduction results from the use of black typewriting on white paper, the opaque pigment is preferably some white pigment selected from the class generally known as prime hiding pigments, which will impart a high degree of opacity to the coating. The preferred pigment for white backgrounds is rutile titanium dioxide, such as Ti-Pure R-510 manufactured by E. I. du Pont de Nemours & Co., Wilmington, Delaware. Suitable pigments include rutile and anatase titanium dioxides, zinc sulfide, zinc oxide, basic lead carbonate or sulfate, lithopone, etc.

It may also be desirable to use as extender pigments silacious materials such as talc, clay, mica, barium sulfate, calcium carbonate, etc.

Suitable colored pigments may also be used for the purpose of matching the coating composition with any base material to which it may be applied.

The solvent for the composition should have a boiling range of from 65 C. to 120 C., and must be capable of dissolving the resinous binder material. The selected solvent preferably should not dissolve the dyes in the ink used in preparing the copy, or at least only to a very small extent. Suitable organic solvents include benzene, toluene, carbon tetrachloride, etc.

It may also be desirable to use as a diluent in the solvent a material such as isopropyl ether.

In the preparation of the coating composition, the amount of pigment should be about 50 to 85 percent by volume of the total solids used. Especially good results are obtained by using 55 to 80 percent by volume of pigment with about 75 percent by volume preferred. If too much pigment is used, for example 90 percent by volume of pigment, the resulting coating will be powdery, have very little adhesion to the surface on which the coating is applied, and chip from the imprinting of the correction thereon. If too small an amount of pigment is used, for example about 40 percent by volume of pigment, the coating will be tacky, have very litle hiding power, and not provide a satisfactory base for the imprintig of corrections thereon.

The amount of solvent should be sufficient to allow good flow-out characteristics and to form a relatively thin film of coating. The optimum and preferred Stormer viscosity of the coating composition is about 69 Krebs units, although satisfactory results can be obtained with a composition having a Stormer viscosity of from about 50 to 75 Krebs units. Compositions having a Stormer viscosity slightly lower than 50 Krebs units are operable. Compositions having a Stormer viscosity above about 75 Krebs units are not operable or satisfactory in that chipping of the coating may occur and the coating does not provide a proper base for imprinting of corrections thereon. It will be obvious that a part of the solvent may evaporate when the composition is in a container, but the proper viscosity may be easily restored by adding suitable amounts of solvent.

The following examples will serve to illustrate compositions of this invention with greater clarity. The pigments and binders are set forth in volumes of solids.

Example I The following materials were mixed together:

Rutile TiO 75 gal. (2620 lb.). Acryloid B72 (methyl acrylatemethyl methacrylate copolymer) (Acryloid B-72 is manufactured by Rohm & Haas Company, Philadelphia, Pennsylvania) 25 gal. (248 1b.). Toluene 135 gal. (975 1b.).

The mixture was ground in a ceramic ball mill for 16 hours until the pigment was thoroughly dispersed; 75 gallons (425 lb.) of isopropyl ether were added slowly and stirred. The resulting solution had a Stormer viscosity of 60 Krebs units.

Example II The following materials were thoroughly .ground in a ceramic ball mill:

Rutile Ti0 50.0 gal. (1750 lb.). Paraplex G-60 22.5 gal. (185 1b.). Cellolyn 102 15.0 gal. 1b.). Toluene 110.0 gal. (795 1b.). Ethyl acetate 108.0 gal. (795 1b.).

Example III The following materials were ground in a ceramic ball mill:

Rutile Ti0 55 gal. (1920 lb.).

Orange shellac 45 gal. (413 1b.).

Methyl alcohol 118 gal. (777 1b.).

Example IV The following materials were ground in a ceramic ball mill:

Rutile TiO 60 gal. (2100 lb.) Vinylite VYHH 40 gal. (453 1b.); Methyl ethyl ketone 553 gal. (3700 lb.).

(Vinylite VYHH is a copolymer containing 87 percent vinyl chloride and 13 percent vinyl acetate and is manufactured by Carbide and Chemicals Company, New York, New York.)

Example V The following materials were ground in a ball mill:

Rutile TiO 60.0 gal. (2100113.). Cellulose acetate 23.6 gal. (260 1b.). Santicizer M-17 13.2 gal. (133 1b.). Santicizer. 8 3.2 gal. (31 1b.). Methyl ethyl ketone 203.0 gal.

(Santicizer M-17 is a methyl phthalyl ethyl glycolate.

Santicizer 8 is a mixture of N-ethyl orthoand paratoluene sulfonamides. Santicizer M-17 and Santicizer 8 are manufactured by Monsanto Chemicals Company, St.

Louis, Missouri.)

Example VI The following materials were ground in a ceramic ball mill Rutile TiO 50.0 gal. (1750 lb.). Pliolite S-5 47.4 gal. (407 1b.). Aroclor 1254 2.6 gal. (20 1b.). Benzene 294.0 gal- (1820 lb.).

(Pliolite S-5 is a styrene-butadiene copolymer and is manufactured by Goodyear Tire & Rubber Company,

Akron, Ohio. Aroclor 1254 is a chlorinated biphenyl containing 54 percent chlorine and is manufactured by" Monsanto Chemical Company, St. Louis, Missouri.)

Example VII The following materials were mixed together in a container holding ceramic balls:

Rutile TiO 43.4 gal. (1518.6 1b.). Acryloid B72 (methyl acrylatemethyl methacrylate copolymer) 14.2 gal. (140.8 lb.). Toluene 59.9 gal. (432.0 lb.).

The mixture was mixed and ground by subjecting the container and its contents to the action of an agitating apparatus for 30 minutes until the pigment was dispersed. At this time 27.7 gallons (200 lb.) of toluene were added and the container and its contents subjected to the action of the agitating apparatus for an additional 15 minutes. The agitating apparatus was of the type described in US. Patent No. 2,109,133 and provided an endwise and coaxial-rotary reciprocation to a shaft having a means attached thereto for holding the material container. This agitating apparatus, commonly called a Red Devil paint conditioner, is sold by Red Devil Tools, Irvington, New Jersey. The resulting solution was then removed from the container and separated from the ceramic balls. This solution had a Stormer viscosity of 62 Krebs units.

Example VIII The followingmaterials were mixed together in a container holding ceramic balls:

Rutile TiO 14.5 gal. (507.4 lb.). Acryloid B-72 (methyl acrylatemethyl methacrylate copolymer) 2.5 gal. (24.8 lb.). Toluene 14.4 gal. (103.8 1b.).

Toluene in the amount of 24.0 gallons (173.3 lb.) was then added and the mixing and grinding continued for an additional 15 minutes. The resulting solution was then removed from the container and separated from the ceramic balls. This solution had a Stormer viscosity of 62 Krebs units.

Example IX The following materials were mixed together in a container holding ceramic balls:

Rutile TiO 43.4 gal. (1518.6 1b.). Acryloid B72 (methyl acrylatemethyl methacrylate copolymer) 15.0 gal. (148.8 lb.). Toluene 58.5 gal. (423.2 lb.).

The mixture was mixed and ground for 30 minutes by subjecting the containerand its contents to the action of the Red Devil paint conditioner. The resulting paste was then removed from the container and separated from the plurality of ceramic balls.

(a) Toluene in the amount of 13.85 gallons (100.0 lb.) and a 1.04 gallon (200.0 lb.) portion of the paste were mixed and ground in a container holding ceramic balls by subjecting the container and its contents for 15 minutes to the action of the Red Devil paint conditioner. The resulting solution was then removed from the container and separated from the ceramic balls. This solution had a Stormer viscosity of 47 Krebs units.

. (b) Toluene in the amount of 4.15 gallons (30.0 lb.) and a 2.08 gallon (400.0 lb.) portion of the paste were mixed and ground in a container holding ceramic balls by subjecting the container and its contents for 15 minutes to the action of the Red Devil paint conditioner. The resulting solution was then removed from the container and separated from the ceramic balls. The resulting solution had a Stormer viscosity of 76 Krebs units.

Example X The following materials were mixed together in a container holding ceramic balls:

Rutile TiO 22.5 gal. (787.3 lb.). Acryloid B72 (methyl acrylatemethyl methacrylate copolymer) 2.5 gal. (24.9 lb.).

Toluene 55.5 gal. (401.3 lb.).

Example XI Compositions having varying amounts by volume of pigment of the total solids were prepared by mixing portions of a composition prepared as in Example X with additional amounts of toluene and Acryloid B-72 solids. These mixtures were mixed and ground in a container holding ceramic balls for 30 minutes by subjecting the container and its contents to the action of the Red Devil paint conditioner.

(a) In this manner 33.2 gallons (500.0 lb.) of the composition of Example X and a mixture of 4.4 gallons (43.6 lb) of Acryloid B72 sol-ids and 6.6 gallons (47.4 lb.) of toluene were mixed and ground to obtain a resulting solution that contained rutile titanium dioxide in the amount of 63 percent by volume of the total solids and that had a Stormer viscosity of 61 Krebs units.

(b) In this manner 33.2 gallons (500.0 lb.) of the composition of Example X and a mixture of 7.7 gallons (76.0 lb.) of Acryloid solids and 15.8 gallons (114 lb.) of toluene were mixed and ground to obtain a resulting solution that contained rutile titanium dioxide in the amount of 51.6 per-cent by volume of the total solids and that had a Stormer viscosity of 61 Krebs units.

(c) In this manner 26.5 gallons (400.0 lb.) of the composition of Example X and a mixture of 9.8 gallons (97.6 lb.) of Acryloid B72 solids and 20.2 gallons (146.4 lb.) of toluene were mixed and ground to obtain a resulting solution that contained rutile titanium dioxide in the amount of 41 percent by volume of the total solids and that had a Stormer viscosity of 61 Krebs units.

Example XII I The following materials were mixed together in a container holding ceramic balls:

Rutile TiO 22.5 gal. (788.0

Piccopale-70 (Piccopale-70 is a hard solid resin polymerization product, having an average molecular weight of about 1100 and a Ball and Ring melting point of about 70 C., that is formed by catalytic reacting a mixture of The following materials were mixed together in a metal container holding a plurality of ceramic balls:

Rutile TiO 22.5 gal. (788.0

lb.). Vistanex MS (isobutylene polymer,

having an average molecular weight range of 8700 to 10,000) (Vistanex MS is manufactured by the Enjay Company, New

York, New York.) 4.08 gal. (31.2

lb.). Toluene 27.7 gal. (200.0

The mixture was ground for 30 minutes by subjecting the container and its contents to the action of the Red Devil paint conditioner. At that time 41.5 gal. (300.0 lb.) of toluene were added and the mixing and grinding continued for an additional 15 minutes. The resulting composition was then removed from the container and separated from the ceramic balls. The resulting composition was a thick paste which could not be brushed in a smooth coat and that contained rutile titanium dioxide in the amount of 85 percent 'by volume of the total solids.

Example XIV The following materials were mixed together in a container holding ceramic balls:

Rutile Ti 22.5 gal. (788.0

lb.). Vistanex MS (isobutylene polymer,

having an average molecular weight range of 8700 to 10,000) 6.41 gal. (49.15

Toluene 27.7 gal. (200.0 1b.).

The mixture was ground for 30 minutes by subjecting the container and its contents to the action of the Red Devil paint conditioner. At that time 55.4 gal. (400.0 lb.) oftoluene were added and the mixing and grinding continued for an additional 15 minutes. The resulting solution was then removed from the container and separated from the ceramic balls. The resulting solution could be brushed and contained rutile titanium dioxide in the amount of 77.8 percent by volume of the total solids.

Example XV When compositions are prepared according to Example I where in place of all or part of the amount of rutile TiO there are used any of the following pigments: anatase TiO or zinc oxide, or lithopone, there are obtained compositions of the invention.

Each of these compositions was tested in the following manner:

Using white paper, a sentence was typewritten using a carbon ribbon. The coating composition was brushed over a portion of the typewritten copy and permitted to air dry for about 30 seconds. Using the same typewriter and ribbon, additional material was typewritten over the coat ed portion of the paper to simulate correction of an error.

The written material was then photographed using a standard copy camera and standard film to obtain a negative. A positive print was then prepared from this negaitve by a conventional duplicating process.

By this test, Examples I through VIII, inclusive, IXa, XIa, XIb, and XV, which illustrate compositions of the invention, produced negatives wherein the typewritten material under the coating was nondiscernible and wherein the additional typewritten material over the coated portion was clear and distinct. A positive print was prepared from each negative, and it was found that it was impossible to distinguish the additional typewritten material from the part which had not been covered over by the coating composition. Several persons, who were asked to point out the corrected portions of the copy, selected portions not coated.

Examples IXb, X, XIc, XII, XIII, and XIV, which are presented for comparison purposes and which are not compositions of the invention, by this test produced both negatives and positive prints from these negatives in which nondesirable defects were obvious and apparent. Each of these negatives and prints disclosed that the additional typewritten material over the coatings was not clear and distinct and in some instances almost completely illegible. Defects in the additional typewritten material ranged from portions of only a' few letters missing to substantial amounts of almost all letters missing. Additionally, the copy material and these negatives and prints revealed that one or more of the following defects was apparent: chipping of the coating, insufficient masking by the coating with typewritten material under the coating being discernible, poor adhesion of the coating to the paper, and powder rubbing off easily or loosely adhering to the coating. Example IXb illustrates that the Stormer viscosity should not exceed about 75 Krebs units; Examples X and XIc illustrate that the amount of pigment should be about 50 to percent by volume of the total solids used; and

Examples XII, XIII, and XIV illustrate that the binder should contain at least one polar group per monomeric unit.

As can be seen by the foregoing description, the composition of this invention provides a means for rapidly correcting typewritten material which is to be photographed for subsequent reproduction. Corrections can be made without removing the paper from the typewriter, and there is no necessity for cutting out portions of the paper and inserting corrections. All corrections are made before the typewritten material is photographed, and no opaquing of the photographic negative is necessary. This results in a very great saving of time.

It is also to be understood that although the invention has been specifically described in relation to typewritten material, it is not to be limited thereby, and can be used for the purpose of correcting any written or printed material or art work.

. What is claimed is:

1. A process, for preparing a copy from a master paper sheet material having markings thereon, including the steps of: Y

(a) applying selectively a coating composition in its liquid application phase over a portion of the master paper sheet material having markings thereon, the coating composition consisting essentially in its liquid application phase of:

(1) an organic solvent having a boiling point within the range of 65 C. to C. in an amount to provide, in said composition, a Stormer viscosity of 50 to 75 Krebs units; and

(2) a solid material consisting essentially of (i) an opaque pigment in an amount of 50 to 85 percent by volume of said solid material, and

(ii) an air drying highly pigmentable, polymeric resin binder, containing at least one polar group per monomeric unit, in an amount of 50 to 15 percent by volume of said solid material, the binder soluble in said solvent and capable of forming a flexible film;

(b) drying the applied coating;

(c) marking on the dried, applied coating;

(d) photographing the sheet material, dried coating,

and marking, thereby producing a negative; and

(e) producing a copy from said negative, whereby said dried, applied coating is a flexible opaque coating which masks underlying markings from producing a contrasting image on the photographic negative, and whereby said dried, applied coating is characterized as being free from forminga contrasting image with said sheet material on said photographic negative and on said copy.

2. A coating composition, for selective application on paper sheet material having markings thereon, consisting essentially in its liquid application phase of:

(a) an organic solvent having a boiling point within the range of 65 C. to 120 C. in an amount to provide, in said composition, a St-ormer viscosity of 50 to 75 Krebs units; and

(b) a solid material consisting essentially of (i) an opaque pigment in amount of 50 to 85 percent by volume of said solid material, and (ii) an air-drying, highly pigmentable, polymeric resin binder, containing at least one polar group per monomeric unit and selected from the group consisting of a methyl acrylate-methyl methacrylate copolymer and a styrene-butadiene copolymer, in an amount of 50 to 15 percent by volume of said solid material, the binder soluble in said solvent and capable of forming a flexible film; said composition consisting essentially, in its applied air dried phase when applied on selected portions of said sheet material, of a flexible, opaque coating which is receptive to marking thereon and which masks underlying markings from producing a contrasting image with said coating on a photographic negative, and which is characterized as being free from forming a contrasting image with said sheet material on a photographic negative of said sheet material. 3. A coating composition, for selective application on paper sheet material having markings thereon, consisting essentialy in its liquid application phase of:

(a) an organic solvent having a boiling point within the range of C. to 120? C. in an amount to provide, in said composition, a Stormer viscosity of 50 to Krebs units; and

(b) a solid material consisting essentially of (i) rutile titanium dioxide in an amount of 50 to percent by volume of said solid material, and (ii) an amount of 50 to 15 percent by volume of said solid material of an air-drying, highly pigmentable, polymeric resin binder consisting essentially of a methyl acrylate-methyl methacrylate copolymer coating resin which is soluble in said solvent and capable of forming a flexible film; said, composition consisting essentially, in its applied air dried phase when applied on selected portions of said sheet material, of a flexible, opaque coating which is receptive to marking thereon and which masks underlying markings from producing a contrasting image with said coating on a photographic negative, and which is characterized as being free from forming a contrasting image with said sheet material on a photographic negative of said sheet material.

No references cited.

NORMAN G. TORCHIN, Primary Examiner.

I. T. BROWN, Assistant Examiner. 

1. A PROCESS FOR PREPRING A COPY FROM A MASTER PAPER SHEET MATERIAL HAVING MARKINGS THEREON, INCLUDING THE STEPS OF: (A) APPLYING SELECTIVELY A COATING COMPOSITION IN ITS LIQUID APPLICATION PHASE OVER A PORTON OF THE MASTER PAPER SHEET MATERIAL HAVING MARKINGS THEREON, THE COATING COMPOSITION CONSISTING ESSENTIALLY IN ITS LIUID APPLICATION PHASE OF: (1) AN ORGAINC SOLVENT HAVING A BOILING POINT WITH IN THE RANGE OF 65*C. TO 120*C. IN AN AMOUNT TO PROVIDE, IN SAID COMPOSITION, A STORMER VISCOSITY OF 50 TO 75 KREBS UNITS AND (2) A SOLID MATERIAL CONSISTING ESSENTIALLY OF (I) AN OPAQUE PIGMENT IN AN AMOUNT OF 50 TO 85 PERCENT BY VOLUME OF SAID SOLID MATERIAL, AND (II) AN AIR DRYING HIGHLY PIRMENTABLE, POLYMERIC RESIN BINDER, CONTAINING AT LEAST ONE POLAR GROUP PER MONOMERIC UNIT, IN AN AMOUNT OF 50 TO 15 PERCENT BY VOLUME OF 